Herbicidal compositions and methods utilizing oxime ethers

ABSTRACT

New oxime ethers and pesticidal and herbicidal preparations containing them are disclosed. The oxime ethers correspond to the formula WHEREIN R1 is a hydrogen atom or a lower alkyl radical; R2 is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical; or wherein R1 and R2 form part of a saturated or unsaturated carbocycle or a 5-, 6- or 7-membered heterocycle; R3 is a nitro, trifluoromethyl, formyl, lower carbalkoxy, sulfamyl or mono- or di-lower alkyl sulfamyl radical; R4 and R5 each is a hydrogen or halogen atom, an amino, mono- or di-lower alkyl amino, lower alkoxy, cycloalkoxy, lower alkythio, nitro, lower carbalkoxy, arythio, lower aralkylthio, or lower alkyl group, or 5-, 6- or 7-membered heterocycle.

United States Patent [1 1 Hubele Nov. 12, 1974 HERBICIDAL COMPOSITIONS AND METHODS UTILIZING OXIME ETHERS Related US. Application Data [60] Division of Ser. No. 46,832, June I6, 1970, Pat. No. 3,733,359, which is a continuation-in-part of Ser, No. 521.413, Jan. 18, 1966, abandoned.

[30] Foreign Application Priority Data Jan. 22, 1965 Switzerland 9l5 July 9, 1965 Switzerland 9630 [52] US. Cl "7'i/i21, '71/9'5, 71/98, 71/103, 71/105, 71/106, 71/107 [51] Int. Cl A0ln 9/20 [58] Field of Search ..71/121,122, 124

[56] References Cited UNITED STATES PATENTS 3,236,889 2/1966 Pawloski 2,997,379 8/1961 Goodhue 2,054,509 9/1936 Pastac 7l/l22 FOREIGN PATENTS OR APPLICATIONS 645,851 9/1964 Belgium 7l/l2l 29,039 [2/1965 Japan 7l/l24 Primary E.\'uminerGlennon H. Hollrah Attorney, Agent, or FirmHarry Falbcr; Frederick H.

Rabin [57] ABSTRACT New oxime ethers and pesticidal and herbicidal preparations containing them are disclosed. The oxime ethers correspond to the formula wherein R is a hydrogen atom or a lower alkyl radical; R is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical; or wherein R and R form part of a saturated or unsaturated carbocycle or a 5-, 6- or 7-membered heterocycle; R is a nitro, trifluoromethyl, formyl, lower carbalkoxy, sulfamyl or monoor di-lower alkyl sulfamyl radical; R and R each is a hydrogen or halogen atom, an amino, monoor di-lower alkyl amino, lower alkoxy, cycloalkoxy, lower alkythio, nitro, lower carbalkoxy, arythio, lower aralkylthio, or lower alkyl group, or 5-, 6- or 7- membered heterocycle.

4 Claims, No Drawings HERBICIDAL COMPOSITIONS AND METHODS UTILIZING OXIME ETHERS CROSS REFERENCE This is a division of application Ser. No. 46,832, filed on June 16, 1970, now US. Pat. No. 3,733,359, which in turn is a continuation-in-part of application Ser. No. 521,4l3, filed .lan. l8, 1966, now abandoned.

BACKGROUND OF THE INVENTION The present invention provides new oxime ethers and pesticidal preparations containing them. The oxime ethers correspond to the formula wherein R, is a hydrogen atom or a lower alkyl radical; R is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical; or wherein R and R form part of a saturated or unsaturated carbocycle or a -,6-or 7-membered heterocycle; R is a nitro, trifluoromethyl, formyl, lower carbalkoxy, sulfamyl or monoor dilower alkylsulfamyl radical; R and R each is a hydrogen or halogen atom, an amino, monoor di-lower alkylamino, lower alkoxy, cycloalkoxy, lower alkylthio, nitro, lower carbalkoxy, arylthio, lower aralkylthio group or 5-, 6- or 7-membered heterocycle.

R, in the above formula stands for a lower alkyl radical. Such radicals contain one to four carbon atoms and may be branched or unbranched such as the methyl and ethyl groups or the normal or iso-propyl or butyl group or secondary or tertiary butyl group. Preferred groups, however, are besides the hydrogen atom the methyl and ethyl radicals.

R stands for an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical. The aliphatic radical may be branched or unbranched, saturate or unsaturated. Preferably such radicals contain up to eight carbon atoms and are alkyl or alkenyl radicals which may be substituted or unsubstituted. Suitable substituents are for instance halogen atoms, such as fluorine, chlorine or bromine or hydroxy or alkoxy groups. The cycloaliphatic radicals contain three to eight carbon atoms and may be saturated or unsaturated and monoor polycyclic. As a rule they contain three to 12 carbon atoms and are saturated. They preferably are monoor bicyclic and have 3 to 7 ring members. The araliphatic radicals contain in the aromatic moiety at least one benzene nucleus and in the aliphatic moiety preferably an unbranches chain containing one to four carbon atoms. This aliphatic chain may be saturated or unsaturated, substituted or unsubstituted. Suitable substituents are hydroxy groups and halogen atoms, such as chlorine and especially bromine. Suitable chains contain two carbon atoms and are saturated; they may also contain one or two bromine atoms or one double bond. Aromatic radicals are to be understood as being substituted or unsubstituted phenyl radicals or condensed ring systems. The preferred embodiment are substituted and unsubstituted phenyl radicals. Suitable substituents on the phenyl moiety are e.g. halogen atoms such as fluorine and especially chlorine, bromine and iodine; lower alkyl and alkoxy groups containing one to four carbon atoms; hydroxy groups; amino groups which may be substituted by one or two lower alkyl, lower alkoxyalkyl or lower alkanol radicals; nitro groups; lower alkyl carbamoyl radicals; phenoxy groups which may be substituted by one or more of the substituents enumerated above for the phenyl radical especially by nitro groups. The heterocyclic radicals coming into consideration particularly are 5- or 6- membered and contain at least one oxygen or sulfur especially however nitrogen atom. These heterocycles may be substituted, preferably by lower alkyl radicals, especially the methyl group. Examples of such heterocycles are i.a. pyridine and quinaldine compounds.

R stands for a trifluoromethyl, formyl, nitro, lower carbalkoxy, sulfamyl or monoor di-lower alkylsulfamyl group. The alkyl moieties of the carbalkoxy and alkylsulfamyl group contain one to four carbon atoms and may be branched or unbranched. Preferred alkyl moieties contain one or two carbon atoms. However, suitable substitutent are not limited to the above enumeration. Thus also halogenalkyl groups quite generally may be used. Moreover, halogen atoms such as chlorine, bromine and iodine; alkyl groups containing one to six carbon atoms, the carboxyl group; lower alkylor aryl-, especially phenylcarbamyl groups; the sulfonic acid groups; and lower alkylsulfonyl groups may be used likewise.

R and R each stands for a hydrogen or halogen atom, a lower alkyl, amino, monoor dilower alkylamino, lower alkoxy, cycloalkoxy, lower alkylthio, lower carbalkoxy, arylthio, lower aralkylthio, nitro or heterocyclic radical. The halogen atoms may be elected from fluorine, bromine, iodine and especially chlorine. The lower alkyl moieties enumerated above contain one to four carbon atoms and may be branched or unbranched. The heterocyclic radicals are 5-, 6- or 7-membered, especially 5- or 6-membered, and contain as heteroatoms one or more oxygen, sulfur or especially nitrogen atoms. Such heterocyclic radicals are i.a. the pyridino and morpholino radical. The cycloalkoxy radicals are 3 to 8-membered, especially however 6-membered. Representative of such radicals is the cyclohexoxy radical. Especially suitable oxime ethers are those which correspond to the formulae wherein R R R R and R have the meanings given above. More particularly R stands for a nitro, trifluoromethyl, formyl, methylcarbonyl, methylsulfamyl or a dimethylsulfamyl radical, R for a hydrogen or chlorine wherein R and R have the above meanings. More particularly R may stand for hydrogen and R for a substituted phenyl radical. Such compounds correspond to the formulae and more specifically to the formulae wherein R R and R have the meanings given above and X and X each stands for halogen. More specifically X represents chlorine bromine and iodine, whereas X stands for chlorine.

The oxime ethers of the formulae (I) to (VI) may be derived from aliphatic, araliphatic, aromatic or heterocyclic aldehydes or ketones, and also from quinones and endocyclic ketones for example fluorenone, indanone, acenaphthenone, anthrone, N-methylpyridone. N-methylpiperidone, furfurol or nitrofurfurol.

Preferred use is made of oxime ethers derived from aliphatic aldehydes or ketones, from araliphatic aldehydes or ketones, or from aromatic or heterocyclic aldehydes or ketones.

Suitable aliphatic aldehydes are simply constituted aldehydes for example acetaldehyde, propionaldehyde, butyraldehyde or aldehydes having a longer chain, for example heptaldehyde, stearaldehyde or unsaturated aldehydes for example crotonaldehyde. Suitable aliphatic ketones are simple ketones for example acetone, methylethyl ketone, hexanone-(3), diisopropylketone, mesi tyl oxide, and phorone. Suitable araliphatic or aromatic aldehydes vand ketones are cinnamic aldehyde, hydrocinnamic aldehyde, halogen adducts or cinnamic aldehyde for example dibromo-cinnamic aldehyde, dii- Odo-cinnamic aldehyde, acetophenone, propiophenone, benzaldehyde, nuclear halogenated, alkylated, nitrated and alkoxylated benzaldehydes. Examples of suitable cyclic ketones are cyclopentanone, cyclohexanone, cycloheptanone as well as their cyano derivatives. Suitable heterocyclic ketones and aldehydes are, for example, picoline aldehyde, nicotine aldehyde, isonicotine aldehyde and N-alkylpiperidones.

If such aldehydes or ketones contain aromatic radicals, their suitably substituted derivatives may likewise be used. These substituents may be of a non-functional kind, for example halogen atoms, nitro or nitroso groups, or of a functional kind or derived from functional substituents, being, for example hydroxyl, acyloxy, carbamoyloxy, alkoxy, aryloxy, thiol, acylthio, alkylthio, trifluoromethyl, cyano, formyl, amino, alkylamino, dialkylamino, arylamino, diarylamino, carboxy or carbalkoxy groups.

By virtue of their borad biocidal spectrum the new oxime ethers offer the special advantage that they are suitable for combating a very wide variety of vegetable and animal pests. They are suitable not only for use as herbicides, which is the preferred utility, but when used in a concentration that does not produce any phytotoxic effects, they are very useful in plant protection for combating harmful micro-organisms, such as phytopathogenic fungi, for example Alternaria salani, Phytophthora infestans and Septoria apii, and act also against harmful insects, acarides, nematodes and their ova and larvae. They may also be used quite generally as microbicides, for example against Aspergillus species, and as insecticides, for example against midges and flies.

The oxime ethers according to this invention may be used per se or in admixture with suitable carriers. Such carriers may be solid or liquid. The pesticidal preparations thus formed may therefore contain a solid carrier, a solvent diluent, dispersant, wetting agent, adhesive, fertilizer and/or other known pesticides.

For the manufacture of solutions of compounds of the general formula (I) for direct spraying there may be used, for example, petroleum fractions of a high to medium boiling range, for example Diesel oil or kerosene, coal tar oil and oils of a vegetable or animal origin, as well as hydrocarbons for example alkylated naphthalenes, tetrahydronaphthalene if desired in conjunction or admixture with xylene mixtures, cyclohexanols, ketones, chlorinated hydrocarbons for example trichloroethane or tetrachloroethane, trichlorethylene, trior tetrachlorobenzene. it is advantageous to use organic solvents boiling above 100C.

Aqueous forms of applications are prepared most advantageously from emulsion concentrates, pastes or wettable spray powders by addition of water. Suitable emulsifying or dispersing agents are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids containing a longchain hydrocarbon residue of about to carbon atoms with ethylene oxide, for example the condensation product of octadecyl alcohol with to mols of ethylene oxide, or of sybean fatty acid with 30 mols of ethylene oxide, or of commercial oleylamine with 15 mols of ethylene oxide, or of dodecylmercaptan with 12 mols of ethylene oxide. From among suitable anionic emulsifiers, there may be mentioned the sodium salt of dodecyl alcohol sulphuric acid ester, the sodium salt of dodecylbenzenesulphonic acid, the potassium or triethanolamine salt of oleic or abietic acid or of mixtures of these acids, or the sodium salt of a petroleumsulphonic acid. Suitable cationic dispersants are quaternary ammonium compounds, for example cetyl pyridinium bromide or dihydroxyethyl benzyl dodecyl ammonium chloride.

For the manufacture of dusting and casting preparations, there may be used as solid vehicles talcum, kaolin, bentonite, calcium carbonate, calcium phosphate, or coal, cork meal, wood meal or other materials of vegetable origin. It is also very advantageous to manufacture preparations in granular form. The various forms of application may contain the usual additives for improving the distribution, the adhesion, the stability towards rain or the penetration; as such substances there may be mentioned fatty acids, resin, glue, casein and alginates.

The preparations of this invention may be used by themselves or in conjunction or admixture with conventional pesticides, especially insecticides, acaricides, nematocides, bactericides or further fungicides or herbicides.

Especially potent herbicides are those preparations which contain as active ingredient a compound of the formula wherein R represents a hydrogen atom or an aliphatic radical and R an aliphatic radical or an unsubstituted or substituted phenyl group, A represents NO CHO, COOH or C00 alkyl, and B stands for hydrogen, -NO COOH, COOalkyl or chlorine. The phenyl radical R may carry various substituents, for example halogen atoms, nitro, alkyl. hydroxyl or alkoxy groups and/or carbamoyloxy groups.

Particularly potent herbicides are the compounds of the formula (Ia) wherein R and R have the following meanings:

Q H N6,

H :HN-C O O-Q- H HO (X=Br 01 I) X H CHr- CzHs- OCH: H smog Especially useful acaricides are those preparations which contain as active ingredient a compound of the wherein R represents a hydrogen atom and R a phenyl radical which may be substituted by halogen atoms or alkyl or alkoxy groups, or wherein R and R represent alkyl radicals or are part of an isocyclic residue.

Especially potent are the compounds of the formula R1 R: H g 1 II CE:

elf: C H- The active ingredients of formula I may be manufactured according to known methods, such as e.g.:

A salt of a ketoxime or aldoxime of the formula I wherein R and R have the above meanings and Me stands for a metal atom, preferably an alkali metal atomis reacted with a halogeno-benzene of the formula Hal wherein R to R have the above meanings and Hal represents a fluorine, chlorine, bromine or iodine atom.

The reaction may be carried out in a solvent, for example in ethanol, methanol, acetonitrile or dioxan, as a rule at room temperature; in many cases it is accompanied by a spontaneous rise in temperature. The oxime ethers obtained in this manner are very easy to isolate by diluting the reaction solution with water. The ethers precipitate and may, if desired, be recrystallized. This process may be varied in that following upon the formation of the oxime ether one or several groups, R R R R are subsequently converted.

More especially, halogen atoms R and/or R may be exchanged for compounds containing active hydrogen atoms, thus for example for ammonia, primary or secondary aliphatic, araliphatic or aromatic amines, alcohols, phenols, alkanethiols or thiophenols.

The oxime ethers accessible in this manner may take the syn-form or the anti-form. As a rule, they are obtained in the form of a mixture of isomers, which can be resolved into the two forms by a usual operation, for example crystallization or adsorption. For the manufacture of the preparations of this invention, it suffices to use the mixture of isomers as obtained by the reaction.

The present invention further includes new oxime ethers of the general formula wherein R and R have the above meanings and R represents a trifluoromethyl, formyl, unsubstituted or substituted carboxyl or possibly alkylated sulphamyl residue, and R represents a hydrogen atom or :1 nitro group, or wherein R stands for the nitro group and R for a possibly esterified carboxyl group.

The following Examples illustrate the invention:

EXAMPLE 1 A solution of sodium ethylate prepared from 11.5 parts of sodium and 500 parts by volume of absolute ethanol is added to 76 parts of anisaldehyde in 400 parts by volume of absolute ethanol. During 10 minutes at 40C 101 parts of 4-chloro-1,3-dinitroben2ene in 300 parts by volume of absolute ehtanol are added drop, the temperature rising to 65C. The batch is cooled to room temperature, diluted with water, filtered and recrystallized from dimethylformamide-l-ethanol. The product melts at 187 l7.5C.

EXAMPLE 2 A solution of sodium ethylate prepared from 13.1 parts of sodium and 300 parts by volume of absolute ethanol is added drop by drop during 30 minutes, at room temperature, to a solution of 82 parts of orthomethoxybenzaldehydeoxime and 115 parts of 4-chloro-1,3-dinitrobenzene in 1,000 parts by volume of acetonitrile. After 4 hours, the batch is diluted with 3,000 parts by volume of water, filtered and recrystallized from toluene+acetone. The product melts at 184 184.5C.

EXAMPLE 3 A solution of sodium ethylate prepared from 18.5 parts of sodium and 500 parts by volume of absolute ethanol is added drop by drop during 30 minutes at room temperature to a solution of parts of cyclohexanone oxime and 162 parts of 4-chloro-1,3- dinitrobenzene in 500 parts by volume of acetonitrile. After 4 hours, the batch is diluted with water filtered and recrystallized from acetonitrile. The product melts at 105.5- 106C.

EXAMPLE 4 A solution of sodium ethylate prepared from 12 parts of sodium and 250 parts by volume of absolute ethanol is added drop by drop at room temperature to a solution of 50.5 parts of methyl-isopropoyl ketonoxime and 101.3 parts of 4-chloro-1,3-dinitrobenzene in 400 parts by volume of acetonitrile, while stirring. After 12 hours, the batch is diluted with water, filtered and recrystallized from acetonitrile. The product melts at 85 to 86C EXAMPLE 5 EXAMPLE 6 An oxime salt solution of 43.5 parts of isobutyraldoxime and 10.5 parts of sodium in 300 parts by volume of absolute ethanol is added drop by drop during 30 minutes at 5C to a mixture of 93 parts of 4-fluoro-l,3-dinitrobenzene and 200 parts by volume of acetonitrile, while stirring. The batch is then stirred for 3 hours at room temperature, diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at 80 to 82C.

EXAMPLE 7 A solution of 54 parts of the cyclohexanone oxime sodium salt in 800 parts by volume of dioxane is added drop by drop at room temperature during 30 minutes to a mixture of 106 parts of 4-chloro-3-nitrobenzenesulphonic acid-( l )-dimethylamide in 500 parts by volume of dioxan while stirring. During the addition, the temperature rises to 35C. After 2 hours, the batch is heated for /2 hour at 50C, then diluted with ice water, filtered, and recrystallized from ethanol. The product melts at 124 to 125C.

EXAMPLE 8 An oxime salt solution prepared from 30 parts of 2- chlorobenzaldehyde oxime, 4.5 parts of sodium and 400 parts by volumeof absolute ethanol is added drop by drop at room temperature, during 30 minutes, to a solution of 42 parts of 5-chloro-2,4-dinitraniline in 500 parts by volume of acetonitrile while stirring. After 6 hours, the whole is diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at 166 to 167C.

EXAMPLE 9 33 Parts of a-methylaminopropionitrile in 200 parts by volume of dioxan are added drop by drop within 1 hour at 50C while stirring to 69 parts of couminaldehyde oxime-O-(5-chloro-2,4-dinitro-phenyl ether) in 700 parts by volume of dioxan, during which the temperature of the solution rises slightly.

After 1 hour, the batch is diluted with ice water, filtered and recrystallized from ethanol+dimethylformamide. The product melts at 161 to 162C.

EXAMPLE 10 =NO NO2 G A..li t

23' Parts of isopropylamine in parts of dioxan are added drop by drop during 1 hour, at 50C, to 77 parts of fluorenone oxime-O-(5-chloro-2,4-dinitrophenyl ether) in 1,500 parts by volume of dioxan. The batch is then refluxed for 3 hours at 80C, another 20 parts of isopropylamine are added and the mixture is heated for 3 hours at 80C, diluted with ice water, filtered and digested with hot dimethylformamide. The product melts at 240 to 241C with decomposition.

EXAMPLE 1 1 An oxime salt solution prepared from 86 parts of 3,4- dichlorobenzaldoxime, 10.3 parts of sodium and 600 parts by volume of absolute ethanol is added drop by drop at room temperature within /2 hour to parts of isopropyl-(5-chloro-2,4-dinitrophenyl)-sulphide in 400 parts by volume of acetonitrile, while stirring. After 3 hours, the batch is diluted with ice water, filtered and recrystallized from acetonitrile. The product melts at 191 to 192C.

EXAMPLE l2 1 1 12 A thiophenolate solution prepared from sodium I TABLE 1 Cominued methylate and 29 parts of 4-chloroth1ophenol in 800 Compound R1 Melting parts by volume of dioxan 18 added drop by drop, under umbe point a current of nitrogen, during 30 minutes, to 63 parts of 2-methoxybenzaldehydoxime-o-(5-chloro-2,4- 5 R2 W dinitrophenyl ether) in 1,000 parts by volume of di- 25 OH 0 CH- 206-5207 oxan, while stirring. The batch is then heated for 1 hour 3 at 40C, diluted with ice water, filtered and recrystallized from dioxan+dimethylformamide. The product 1 melts at 197 198C. -N02 The following oxime ethers of 2,4-dinitrophenols have been prepared by analogous methods described in the foregoing Examples:

N02 111 R;\ 2 26 CH: 142444 C=N-O NO2 27 CH3 71-715 C: i T851151 4.

28 141-142 Compound R1 Melting 2 s)2 -CH= number point o: 9* c 29 0 C II: 148. 5-144 R2 18 1. 01 165-166 c41150-o11= (}H= 30 0 CH3 175-175. 5 14 Q 195-196 CH1 OH= c1- -CH= 31 CH3 195-196 15 Cl 197-197. 5 Q I a2 (3H3 180-181 16 186-187 Q-c:

(CH8)2N -CH: 35

33 CH3 17 N09 189-1995 CH3(CH2)C: @4111: 84 1111 1985-199 18 1. (H) 181-182 Q cmNH-c 0--on= N09 36 111; 8989.5 OH= CHg-C:

. H m 21 (3H3 165-166 1 31 196-197 CH CH: HO-Q-OH: CH3

38 3111 47-48 23 O CH; 202 2o CH3 (CH2) 5-C:

l 39 CH3 CH7 85-97 0CH= \C-CH2 CH2 0: N02

(|J=CH CH5 0112-4) 24 Cl 184-185 011 0Q c= I CH C\ I TABLE 1-'-C( )ntinu e d TABLE 1- Con!inued Compound R1 Meltin Co d number poin? nufi y R'\ 213??? 0.) c: (1. R2 R2 41 N0 205-206 5 58 2mm OrN-Q-CH: c1- -0 crr=c1r-cm 42 311; 107-109 CH. C 60 Cm 155 151;

CH3 O(CH3)2 C: z:

CH CH:

43 II 188-1 61 CH=-CH= 17.3-90.5 Q 61a 01 m-ws s H0 CH:

'44 Q. (CHaMCH-CEz 75-77 01 /C= Ye1!0woil. Decomp. W (CHa)2CH-CH2 45 CHPCHQ 81 The following oxlme ethers of 2,4-d1n1tr0-5- C chlorophenol were prepared by methods analogous to those described in the foregoing Examples: CH2 I CH CH:

/c= -0-NO2 C2H5 B2 E3] 47 OH CH2 91-92 011345-011 TABLE 2 Ha R1 8 m 48 (EH3 0 Ha 36.37 3 5 Compound pong CHaCHCH number R2 0 Q) 62 CH 49 CH3 (3H1 56-58 130-131 CH CH: CHaH(CH2)2- Q N CH= 63 CH: 92-94 51 CH: 161-163 CH;

01130 -CH= N/ OCH: s0 53 CIEHa CH; -131 66 .2 ('JH; 72.74

CHa-C=CHJJ= C2H5G= 54 EH3 136-142 67 G1 a 186-187 CH=CH CH 183-184 50 a Cl @CHBr-CHBI- 0 68 Celia 126-127 GH2- c c 2 C(CHrDa/C: Q 07 57 185-186 65 so -176 TAB IIE E i-Continued TABLE 4- Continued R1 R1 I v C: Melting 4 C: Melting point. point Compound number R: C.) Compound number R2 C a 5 0 U6 0 CH3 143-144 107 .L 121-122 0 /CH 4311: CH

10 10s (I111: 131-132 H0 ()H:

96b Br 1 181-182 \\N 100 NO: 156-157 110-- -CH: l

C J( 1)3 110- -c1r= 111 1. CH1 CH1 CHa-H-(CHzh-:

Brown oil. Decomp. 112 1k Cz 5- The followmg oxlme ethers of 2,4-d1n1tr0-6-carm CH 1 1 14 bomethoxyphenol were prepared in a similar manner: (1} 3 4 3 N 02 114 OH; 02115 0) /C=N0 N02 (g R 2 b 0 0 CH: 1146 ljr 165-167 TABLE 4 no- -cn I R'\ m C: Melting fl Point The followmg oxrme ethers of 2,4-d1n1tro-6-carboxy- (Jompound number R2 C.)

clohexoxyphenol were prepared 1n a slmllar matter: 97 124-126 i flv 1 1 01 on: N02

40 as 50-51 0:11-0- N02 1 R2 00 Cl 105-107 0-/ H R 1 c: M 11 100 -1 01 123 121 0126 Compound number R2 C.)

CH= 115 01 130-132 "T0110" c -cnz @011: 116 cg: 122-123 102 CH3 65-67 GHQ-( CH3 117 111-11 103 aC a (3-011: 3

CHa- --C= H3 118 EH CH3 P 104 CH; cm 6) O 0H;- H-om- CH3 105 CH3 141443 19 C2H5 (I) CH=CH-1I= OH: Brownoll.

Furthermore, the following oxime others 01' 2-nitro-4- formylphenol were prepared analogously:

C=NO- O HO TABLE 6 O: Melting point Compound number R2 C.)

HO-CH= H O-CH= Decomp.

Furthermore, the following oxime ethers of 2-nitro-4- trifluoromethylphenol were prepared analogously:

/C=NO C F3 R2 TABLE 7 /C: Moltling n1 Compound number R: U l23 (H1 J 3 1I1 ounoQ-u 11 CH-C C 3 CH HO- -CH= HO -CH= e Decomp.

trinitrophenol were manufactured analogously:

i it

(J: Moltnnt point. Compound number R2 1 -1 CH3 I0 The following oxime ethers of 2-nitro-4-N,N-dimethylsulphamylphenol were manufactured analogously:

H ,Nbg W V 7 R C=NO SO2N(CH3)2 TABLE 8 C: Melting point Compound number R C.)

HO CH:

132;-..L:QLYIT IIIIII 142-144 a CH, ;C

CH2 CH3CCH3 C:

CHCH2 133 CH3-CHC= 111-113 Deoomp.

The cyclohexanone 0x1me-2-nitro ifi methylsulphamylphenyl ether (compound 134) melts at 129 TABLE 9 The following oxime ethers of 2,4-dinitro-- B1 isopropylaminophenol were manufactured analoo= Melting y m Compound number R; 8C.) N 02 5 R1 135 21 \C=N.-O No;

n 1111011110 136 149-150 2 s)2 CH:

' l0 TABLE 137 om-on c= 190-200 R| Ha 43H: Melting Compound gull-1t 138 CHg-CH-(OH h-C: 113-114 number R: C.)

139 -Q 0111-0112 187-188 CH:

0111-011; /C=CH 0 CH3 15s s C:

o-cm C OH; on,

Deoomp. 25 0- The following oxime ethers were also manufactured in an analogous way to that described above HO CH=NOQ-NO2 bl CzHs 14a 11 N01 157-158 110- c11=N-0-som omcmcm)1 II0CH=NO-NO2 l B1- Hz HOOH=NO NO2 v I H3 149 CH2C H2 Oll Continued Com and nurn r Formula EXAMPLE l3 IIIOz a. A mixture of 50 g of the active ingredient No. 14, 20 g of l-lisil (a silica preparation), 25 g of kaolin, 3.5 g of flotation agent (for example a condensation product of 1 mol of para-octylphenol with 6 to 10 mols of ethylene oxide) and 1.5 g of a wetting agent (for example the sodium salt of l-benzyl-2-heptadecylbenzimidazole-disulphnoic acid) is finely ground to form a wettable powder containing 50 percent of the active product.

The active ingredient No. 21 is formulated in a similar manner, except that 25 g of chalk are used instead of 25 g of kaolin. In an identical manner, the active substance No. 14 of Example 4 is formulated.

b. 500 Grams each of the active ingredients Nos. 5 and 67 are mixed with l g of ammonium lign insulphonate, 45 g of dicresyl methanedisulphonic acid, 10 g of a mixture of 40 percent of an alkylarylpolyether alcohol and 60 percent of magnesium carbonate, and

335 g of kaolin. In each case, the resulting mixture may be diluted with water to form a stable emulsion.

EXAMPLE 14 5.0 kg each of the active compounds listed below 12 days after sowing, when the plants had developed 1 to 2 genuine leaves.

The following results were recorded:

Species Comp. No. No. No. No. No. No. No. No. No. No. No. of plant No.1 2 l3 l4 l5 17 18 19 21 26 27 29 Beta vulgaris 9 9 9 9 9 l0 l0 9 l0 l0 l0 l0 Calendula 9 l0 l0 l0 l0 l0 l0 l0 8 l0 l0 9 Linum l0 8 8 l0 l0 l0 l0 l0 8 l0 l0 l0 Brassica 9 l0 l0 l0 9 l0 l0 9 l0 l0 l0 l0 Dautus 9 l0 l0 9 2 8 l0 l0 8 9 8 2 Lacruca l0 l0 l0 l0 2 5 l0 l0 l0 l0 l0 2 Medicago 2 4 4 l0 6 l0 l0 9 l0 l0 l0 l0 Soya l 2 9 l0 1 4 8 7 8 4 l l Tririrum 0 0 0 l 0 O 0 0 0 l l l Hordeum 2 l 2 0 2 3 3 2 l 3 2 l Sorghum l l O l l 2 4 l 2 2 l l Phaseolus 4 9 5 4 2 6 5 9 7 4 5 1 Species Com No. No. No. No. No. No. No. No. No. No. of plant No. 2 33 36 37 41 43 46 47 56 62 65 Beta vulgarir 9 8 l0 l0 l0 l0 l0 l0 l0 l0 l0 Calendula' 8 7 l0 9 l0 I0 10 10 8 l0 l0 Linum l0 7 l0 l0 l0 8 9 9 7 l0 l0 Brassica l0 8 l0 l0 l0 l0 l0 l0 l0 l0 l0 Daucus l0 6 l0 9 9 8 8 l0 8 8 6 Lacluca 8 5 l0 9 l0 l0 l0 l0 9 8 8 Medicago 2 2 2 3 6 l0 l0 l0 6 8 9 Suya 0 0 0 0 0 8 l l 6 l 1 Triricum 0 O 0 0 0 0 l 0 0 0 I Hordeum 2 l l l 0 O l 0 0 0 0 Sorghum l l 2 2 l O O l 0 0 l Phaseolus 4 7 8 4 5 8 4 2 4 l 4 S ecies of No. No. No. No. No. No. No. No. No. No. No. No. No. No. pant 71 72 88 9l 92 93 97 98 100 10! 109 121 i151 Beta vulgaris l0 l0 l0 8 8 l0 8 l0 l0 l0 l0 8 l0 8 Calendula l0 l0 l0 8 l0 l0 l0 l0 l0 l0 8 7 8 l0 Linum l0 l0 l0 8 l0 8 l0 l0 l0 l0 8 8 l0 l0 Brassica l0 8 l0 l0 l0 8 8 l0 l0 8 8 l0 8 6 Deucus 6 l0 I0 9 5 10 8 l0 8 8 8 l0 l0 l0 Lavruca 8 l0 l0 9 l0 8 5 l0 8 l0 l0 9 l0 l0 Medicagu l0 8 l 0 6 V l0 l0 l0 l0 8 l0 l9 l0 8 8 o ued s l w 7 r Species of No. No. No. No. No. No. No. No. No. No. No. No. No. No. plant 71 72 88 91 92 93 97 98 100 101 109 121 130 131 Soya 1 1 1 5 s 10 s i 1 s s 2 10 1o Trilicum 0 l 0 l 0 l 1 l 0 0 0 O 0 Hurdeunt O O O l O O 0 l O 1 l l l l Sorghum 2 2 l 0 1 0 l 0 l 0 0 0 l l Plraseolus 8 6 7 4 7 8 8 5 1O 1O 6 4 5 Explanation: 0 no effect 5 damage that spreads 5 damage that results in the plant dying off plant completely destroyed.

Each of the active compounds Nos. 5, 10, 20, 56, 67, 88 and 99, formulated as described in Example 13b was sprayed on the soil in an amount of 0.5 kg per hectare, in a greenhouse test immediately after sowing i.e. by the preemergence method. The test plants and the results achieved are listed in the following Table:

Accordingly, the two new active substances may be used as total herbicides by the pre-emergence method or, when used in a suitable concentration, for the selec- |5 tive control of weeds, for example in grain crops (Triticum and Hordeum varieties of cabbage (Brassica) and leguminoses (soybeans and phaseolus beans).

S ecies of Comp. p ant 0.5 No.10 No.20 No.56 No.67 No.88 No.99

Trilicum 2 2 2 2 2 l l Hordeum 2 2 l 1 2 2 1 Avena l0 8 8 8 8 10 8 Fan 10 10 l0 l0 10 10 8 Dactylis 1O 1O l0 10 1O 1O 1O Linum 3 3 5 5 3 5 l0 Brarsica 3 3 2 2 l 0 0 Lacluca 10 8 8 l0 1O 1O 10 Medicagu 4 5 8 8 8 l0 8 lya l l 1 l l 0 0 Phaseolus l 1 O l 0 l 0 0 no effect 10 plant completely destroyed When applied in an amount of 0.5 kg of active compound only a few plants were strongly affected, above all Avena, Poa, Dactylis and Lactuca, whereas the others were not damaged at all or only to a very small extent, such as Triticum, Hordeum, Brassica, Soya and Phaseolus. r

b. The active substances Nos. 5 and 67, formulated as described in Example 13b, in an amount of 4.0, 2.0, 1.0 and 0.5 kg of active substance per hectare, were sprayed over the soil in a greenhouse test immediately after seeding, that is to say, by the pre-emergence method. The seedlings treated and the results achieved are shown in the following Table:

Active substance No. 5

EXAMPLE 15 EXAMPLE 16 10 to Grams of each of the compounds 68, 73, 75, 98 76 and 94 are made up with an adequate amount of an emulsifier (sulphonate-nonionic mixture) in xylene to a volume of ml. These emulsion concentrates Active substance No. 67

4 2 l 0.5 kgAS 4 0.5 kgAS Trilicum 10 10 9 2 l0 7 7 2 Hordeum 10 5 5 2 1O 4 5 2 Avena 10 10 10 10 10 10 10 8 Pen 10 10 10 10 10 l0 10 10 Dactylis 10 10 10 10 l0 l0 10 10 Linum 10 10 10 3 l0 9 8 3 Brassica l0 l0 5 3 10 4 2 1 Lactuca 10 10 10 10 10 10 10 10 Medicago 10 10 10 4 10 10 10 8 Soya l0 7 4 l 9 4 2 1 Phaseolu: 5 1 l l 4 l 0 0 O no effect 10 plant completely destroyed When applied in an amount of 4.0 kg per hectare both these products of the invention displayed a broad effect, whereas with 0.5 kg of active substance only some plants were strongly effected, above all Avena, Poa, Dacrylis and Lactuca, whereas others were not damaged at all or only very little, for example Triticum, Hordeum, Brassica, Soya and Phaseolus.

may be diluted with water to the desired concentration and used as fungicides.

EXAMPLE 17 The products of this invention, for example compound No. 16, are also distinguished by their action against genuine powdery mildew. Zucchetti plants (Cucumis pepo) were trained in a greenhouse and once sprayed prophylactically with a broth containing as active ingredient 0.2 percent of the preparation formulated as described in Example 15. 2 Days after having been sprayed, the plants were infested with spores of 5 Erysiphe cichoracearum and 12 to 14 days later checked for fungus attack. Compared with the untreated control (effect: nil) the sprayed plants displayed a 90 percent effect without having developed phytotoxic damage.

Effects similar to those against Erysiphe cicoracearum described above were observed with the following compounds, which were readily tolerated by the Zucchetti plants:

Compound No. Effect in so 4 I00 49 95 66 20 EXAMPLE 18 The action of the compounds of this invention 25 against leaf spot fungi was confirmed on celery (Apium graveolr'ns) with the fungus Septoria apii. Celery plants were trained in a greenhouse and 2 days before infection with the fungus Seproria, sprayed with broths each containing 0.2 percent of one of the active compounds m mentioned below. After infection, the plants were placed for 2 to 3 weeks in an incubation room having a high atmospheric humidity and then checked for in-. festation against an untreated control series, which latter revealed a nil-return. The effects produced by the compounds of this invention are listed in the following Table:

Compound No. Effect in 4 93 66 100 68 94 73 100 75 92 9s 9 76 100 94 87 so 100 EXAMPLE 19 Herbicidal effect in the greenhouse Preemergent Postemergent compound No.99 compound No.93 kgAS 2.0 1.0 0.5 0.25 5.0 2.5

Triticum l0 l0 9 7 0 0 Hordeum l0 9 7 4 0 0 Avena l0 l0 l0 l0 1 l Sorghum 3 2 l 2 l Panicum l0 l0 8 1 l0 8 Pm: l0 1O 10 8 6 2 Dncrylis l0 l0 l0 l0 4 2 Digilariu l0 l0 4 l 7 4 Bela 10 l0 l0 l0 l0 l0 Calendula l0 l0 l0 l0 l0 l0 Linum l0 l0 l0 5 l0 l0 Brassica l0 l0 7 8 l0 10 Daucus l0 l0 l0 l0 l0 l0 Lactuca 10 l0 I0 1o 10 10 Suya l0 8 2 0 4 3 Phaseolus l0 10 l 0 8 5 When compound No.99 was applied in an amount of 2 kg or over, it displayed total herbicidal properties.

When a small amount, for example 0.25 kg, of the active substance of this invention is applied, numerous test plants can be completely or almost completely destroyed without affecting, for example, soybean or phaseolus bean plants. With even smaller amounts wild oats (Avena fatua) in barley (Hordeum) may be controlled.

Compound No.93, applied in an amount of 2.5 kg, was successfully applied against numerous dicotyledons and Panicum, whereas the various types of grain crops were not damaged by the active substance of the invention.

EXAMPLE 20 Test on Grain Crops in the Field In a field of winter wheat which had just been tilled and in which the weeds had reached the 4-leaf stage, the compounds Nos. 18 and 26 were sprayed in an amount of 8.0 kg per hectare. 3 Weeks after the treatment, the effects achieved on weeds were found to be very good (that is to say value 1 and 2 respectively). Grain crops, on the other hand, had not been damaged (value l-2).

Test on Salad in the Open The compound No. 27 was sprayed in an amount of 8.0 kg per hectare on salad four weeks after seeding (3-4 leaf stage) and when the weeds had reached the stage of the large rosette.

The effect achieved on the weeds was good (value 3), whereas the salad was not affected by the herbicide of this invention.

Tests with Marrow Cabbage in the Open Immediately after seeding marrow cabbage and before the weeds had emerged, the soil surface was sprayed with the compounds Nos. 5 and 67 of this invention each being used in amounts of 2.0, 3.0 and 4.0 kg per hectare. The effect achieved and the tolerance observed are shown in the Table, where the following values are used: For effect on weeds 1 very good, 9 effect nil. For tolerance by culture plants: I very good, 9 total destruction.

Amount used Compound No. 5 Compound No. 67

All compounds to be tested were formulated in the usual manner.

To check their acaricidal effect, Phaseolus plants in the 2-leaf stage were infested 12 hours before the treatment by covering them with pieces of leaves infested by a mite species (Tetranychus telarius or Tetranychus urticae; carmine red mite). 12 Hours later, the test plant was found to be covered with mites in all stages of development. The active ingredient, in the form of an emulsion, was sprayed with the aid of a fine sprayer over the plants in a manner such that a uniform layer of droplets was forme on the leaf surface. The mortality was checked 2 and 7 days later and expressed in per- Ova Larvae Adults Comp. After 2 days I% 100% No. I After 7 days 100% 100% 100% 2 do. 2 do. I00% 100% do. 7 do. 100% 100% 100% 3 do. 2 do. 100% 100% do. 7 do. 100% 100% 100% 4 do. 2 do. l00% l00% do. 7 do. I00% I00% l00% 5 do. 2 do. I0()% I00% do. 7 do. I00% 100% I00% I3 do. 2 do. 100% 100% do. 7 do. 80% 100% 100% I4 do. 2 do. 100% 100% do. 7 do. 100% 100% I00% I5 do. 2 do. 100% I00% do. 7 do. 90% 100% 100% 29 do. 2 do. 100% 100% do. 7 do. 100% 100% 100% 31 do. 2 do. I00% 100% do. 7 do. 80% 100% 100% 45 do. 2 do. 100% 100% do. 7 do. 80% 100% 100% 46 do. 2 do. 100% 100% do. 7 do. I00% 100% 100% 58 do. 2 do. l00% 100% do. 7 do. 80% l00% 100% 72 do. 2 do. 100% 100% do. 7 do. 80% I00% 100% 78 do. 2 do. 100% 100% I do. 7 do. 100% 100% 100% 91 do. 2 do. 100% I00% do. 7 do. I00% 100% 100% I01 do. 2 do. 100% 100% do. 7 do. 100% I00% 100% I I5 do. 2 do. 100% 100% do. 7 do. 100% I00% 100% I23 do. 2 do. I00% 100% do. 7 do. l00% 100% 100% Compound No. 4, applied in a concentration of 0.05 percent, displayed a good killing effect against red spiders, for example against Pdrioriy ciiiis alifiiiiotetiahychus tiliae a good killing effect, in fact against both their ova and the postembryonal stages.

The following compounds show at concentrations of 0.05 percent the following mortality rate (ovicidal effect) against panonychus ulmi. (control after 7 days) Compound No. Mortality rate in 9 100 10 I00 21 I00 56 I00 62 80 78 I00 82 I00 88 I00 95 I00 I19 I00 I29 I00 In the following tables also Tetranychus urticae which is resistent to phosphorus acid esters is listed.

5 Compound No. 153 a) action against Terrv urlicue Mortality after 2 days after 7 days Conc. (ppm) Larvae Adults Ova Larvae Adults 800 I00 I00 I00 I00 I00 400 I00 I00 I00 I00 I00 200 I00 I00 80 I00 I00 I00 I00 0 80 80 h) action against Telmelarius Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 I00 I00 I00 I00 I00 400 I00 I00 I00 I00 I00 200 I00 I00 80 80 I00 I00 I00 I00 0 60 80 Compound No. I54 a) action against Tetnurlicae Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 I00 I00 60 I00 I00 400 I00 I00 0 80 I00 200 I00 I00 0 60 80 I 00 I00 I 00 0 0 80 b) Action against (err. It'larizm' Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 I00 80 0 I00 I00 400 I00 80 0 I00 I00 200 I00 80 0 80 80 Compound No. I55 a) Action against Temurticae Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 I00 I00 60 I00 80 400 I00 I00 0 80 I00 200 I00 I00 0 0 I00 b) Action against Terr. Ielarius Mortality after 2 days after 7 days Conc. ppm Larvae Adults Ova Larvae Adults 800 I00 80 0 I00 I00 400 I00 80 0 80 80 200 80 80 0 0 80 Compound No. I56 a) Action against Telnurricae Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 I00 I00 I00 I00 I00 400 I00 I00 I00 I00 I00 200 I00 I00 80 I00 I00 I00 I00 I00 60 80 I00 (ompound No. I56 -Cntinued b) Action against Terr. lclarius Mortality after 2 days after 7 days Coneppm Larvae Adults Ova Larvae Adults 800 100 100 100 I00 100 400 100 100 100 lOO 100 Compound No. 157 a) Action against Tetmlrticae Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 I00 I00 60 I00 100 400 [00 80 80 80 100 200 80 80 60 8O 80 100 80 60 0 60 60 b) Action against Terr. telarius Mortality after 2 days after 7 days Coneppm Larvae Adults Ova Larvae Adults 800 l ()(l 80 80 80 l ()0 400 lllll 80 R0 80 fill 200 ill) 80 (it) 60 80 I00 (10 0 (l O 60 Compound No. 159 a) Action against Tetnurlicae Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 80 80 60 I00 100 400 80 80 60 80 100 200 80 80 60 60 O 100 80 80 0 O 0 b) Action against Terr. telarius Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 80 80 80 100 lOO 400 80 80 8O 80 I00 200 80 60 60 60 0 I00 60 0 0 0 0 Compound No. I60 a) Action against Tetnurticae Mortality after 2 days after 7 days Conc.ppm Larvae Adults Ova Larvae Adults 800 100 100 80 I00 100 400 100 I00 80 100 I00 200 I00 lOO 80 100 [O0 100 I00 I00 60 80 100 h) Action against Tz'rrJe'luriux Mortality after 2 days after 7 days Concppm Larvae Adults Ova Larvae Adults 800 l()() 100 80 100 I00 400 I00 100 80 100 100 200 100 100 60 80 100 l()() 100 100 60 80 100 EXAMPLE 22 Compound No. 4, applied in a concentration of0.05 percent, displayed a good killing effect against red spiders, for example against Panonychus ulmi, Eotetranychus tiliae in fact against both their ova and the postembryonal stages.

Equally good results were observed with compounds Nos. 21 and 3.

EXAMPLE 23 Concentration of active substance in ppm I000 500 250 125 62.5

7!- killcd I00 I00 Hill lllil I claim:

1. A composition for controlling undesired plant growth which comprises l as active ingredient, a herbicidically effective amount of a compound of a the formula wherein X is chlorine, bromine or iodine, and (2) an inert carrier.

2. A method for controlling undesired plant growth which comprises applying to said plant growth a herbicidally effective amount of a compound of the formula wherein X is chlorine, bromine or iodine.

3. The method of claim 2 in which, in the compound,

X is bromine.

4. The method of claim 2 in which, in the compound, X is iodine. 

1. A COMPOSITION FOR CONTROLLING UNDESIRED PLANT GROWTH WHICH COMPRISES (1) AS ACTIVE INGREDIENT, A HERIBICIDICALLY EFECTIVE AMOUNT OF A COMPOUND OF A THE FORMULA
 2. A method for controlling undesired plant growth which comprises applying to said plant growth a herbicidally effective amount of a compound of the formula
 3. The method of claim 2 in which, in the compound, X is bromine.
 4. The method of claim 2 in which, in the compound, X is iodine. 